Correlating the Diffusion of Water to Performance in Model Reverse Osmosis Polyamides with Controlled Crosslink Densities.

We systematically reduce the cross-link density of a PA network based on m-phenylene diamine by substituting a fraction of the trifunctional trimesoyl chloride cross-linking agent with a difunctional isophthaloyl analog that promotes chain extension, in order to elucidate robust design cues for improving the polyamide (PA) separation layer in reverse osmosis (RO) membranes for desalination. Thin films of these model PA networks are fully integrated into a composite membrane and evaluated in terms of their water flux and salt rejection. By incorporating 15 mol % of the difunctional chain extender, we reduce the cross-link density of the network by a factor of two, which leads to an 80 % increase in the free or unreacted amine content. The resulting swelling of the PA network in liquid water increases by a factor of two accompanied by a 30 % increase in the salt passage through the membrane. Surprisingly, this leads to a 30 % decrease in the overall permeance of water through the membrane. This conundrum is resolved by quantifying the microscopic diffusion coefficient of water inside the PA network with quasi-elastic neutron scattering. In the highest and lowest cross-link density networks, water shows strong signatures of confined diffusion. At short length scales, the water exhibits a translational diffusion that is consistent with the jump-diffusion mechanism. This translational diffusion coefficient is approximately five times slower in the lowest cross-linked density network, consistent with the reduced water permeance. This is interpreted as water molecules interacting more strongly with the increased free amine content. Over longer length scales the water diffusion is confined, exhibiting mobility that is independent of length scale. The length scales of confinement from the quasi-elastic neutron scattering experiments at which this transition from confined to translational diffusion occurs is on the order of (5 to 6) Å, consistent with complementary X-ray scattering, small angle neutron scattering, and positron annihilation lifetime spectroscopy measurements. The confinement appears to come from heterogeneities in the average inter-atomic distances, suggesting that diffusion occurs by water bouncing between chains and occasionally sticking to the polar functional groups. The results obtained here are compared with similar studies of water diffusion through both rigid porous silicates and ion exchange membranes, revealing robust design cues for engineering high-performance RO membranes.

The Projectile Perforation Resistance of Materials: Scaling the Impact Resistance of Thin Films to Macroscale Materials.

From drug delivery to ballistic impact, the ability to control or mitigate the puncture of a fast-moving projectile through a material is critical. While puncture is a common occurrence, which can span many orders of magnitude in the size, speed, and energy of the projectile, there remains a need to connect our understanding of the perforation resistance of materials at the nano- and microscale to the actual behavior at the macroscale that is relevant for engineering applications. In this article, we address this challenge by combining a new dimensional analysis scheme with experimental data from micro- and macroscale impact tests to develop a relationship that connects the size-scale effects and materials properties during high-speed puncture events. By relating the minimum perforation velocity to fundamental material properties and geometric test conditions, we provide new insights and establish an alternative methodology for evaluating the performance of materials that is independent of the impact energy or the specific projectile puncture experiment type. Finally, we demonstrate the utility of this approach by assessing the relevance of novel materials, such as nanocomposites and graphene for real-world impact applications.

Studying the high-rate deformation of soft materials via laser-induced membrane expansion.

Cavitation is a phenomenon that occurs when the internal pressure of a material exceeds the resistance to deformation provided by the surrounding medium. Several measurements, such as the blister test, bubble inflation, and cavitation rheology, take advantage of this phenomenon to measure the local mechanical properties of soft materials at relatively low deformation rates. Here, we introduce a new measurement called laser-induced membrane expansion (LIME) that measures the shear modulus of a thin membrane at high strain rates (≈106 s-1 to 108 s-1) by using laser ablation to rapidly expand a thin (tens of microns) elastomeric membrane. To demonstrate the capabilities of this measurement, we use LIME to study the mechanical properties of poly(dimethylsiloxane) (PDMS) membranes at several thicknesses (from 10 µm to 60 µm) and crosslink densities. We find that the shear modulus of the PDMS measured by LIME was weakly dependent on the crosslink density, but was strongly strain rate dependent with values ranging from 106 Pa to 108 Pa. This measurement platform presents a new approach to studying the mechanical properties of soft but thin materials over a range of deformation rates.

Tuning the mechanical impedance of disordered networks for impact mitigation.

Disordered-Network Mechanical Materials (DNMM), comprised of random arrangements of bonds and nodes, have emerged as mechanical metamaterials with the potential for achieving fine control over their mechanical properties. Recent computational studies have demonstrated this control whereby an extremely high degree of mechanical tunability can be achieved in disordered networks via a selective bond removal process called pruning. In this study, we experimentally demonstrate how pruning of a disordered network alters its macroscopic dynamic mechanical response and its capacity to mitigate impact. Impact studies with velocities ranging from 0.1 m s-1 to 1.5 m s-1 were performed, using a mechanical impactor and a drop tower, on 3D printed pruned and unpruned networks comprised of materials spanning a range of stiffness. High-speed videography was used to quantify the changes in Poisson's ratio for each of the network samples. Our results demonstrate that pruning is an efficient way to reduce the transmitted force and impulse from impact in the medium strain rate regime (101 s-1 to 102 s-1). This approach provides an interesting alternative route for designing materials with tailored impact mitigating properties compared to random material removal based on open cell foams.

Controlling toughness of polymer-grafted nanoparticle composites for impact mitigation.

Toughness in an entangled polymer network is typically controlled by the number of load-bearing topological constraints per unit volume. In this work, we demonstrate a new paradigm for controlling toughness at high deformation rates in a polymer-grafted nanoparticle composite system where the entanglement density increases with the molecular mass of the graft. An unexpected peak in the toughness is observed right before the system reaches full entanglement that cannot be described through the entanglement concept alone. Quasi-elastic neutron scattering reveals enhanced segmental fluctuations of the grafts on the picosecond time scale, which propagate out to nanoparticle fluctuations on the time scale 100s of seconds as evidenced by X-ray photon correlation spectroscopy. This surprising multi-scale dissipation process suggests a nanoparticle jamming-unjamming transition. The realization that segmental dynamics can be coupled with the entanglement concept for enhanced toughness at high rates of deformation is a novel insight with relevance to the design of composite materials.

Using microprojectiles to study the ballistic limit of polymer thin films.

The dynamic impact between a particle and a planar material is important in many high impact events, and there is a growing need to characterize the mechanical properties of light-weight polymeric materials at dynamic loading conditions. Here, a laser-induced projectile impact test (LIPIT) is employed to investigate the ballistic limit (V0) and materials properties at impact velocities ranging from 40 m s-1 to 70 m s-1. An analytical expression describing the various energy dissipation mechanisms is established to estimate the yield stress and elasticity for polycarbonate thin films. This measurement approach demonstrates the utility of using low sample mass for discovery of materials for impact mitigation, as well as high-throughput mechanical characterization at dynamic loading rates.

Entanglement Density-Dependent Energy Absorption of Polycarbonate Films via Supersonic Fracture.

The fracture behavior of glassy polymers is strongly coupled to molecular parameters such as entanglement density as well as extrinsic parameters such as strain rate and test temperature. Here we use laser-induced projectile impact testing (LIPIT) to study the extreme strain rate (≈107 s-1) puncture behavior of free-standing polycarbonate (PC) thin films. We demonstrate that changes to the PC molecular mass and the degree of plasticization can lead to substantial changes in the specific puncture energy. We relate these changes to the alteration of the entanglement density of the polymer that determines the underlying failure mechanism as well as the size of the deformation zone.

Self-Assembly of ABC Bottlebrush Triblock Terpolymers with Evidence for Looped Backbone Conformations.

Bottlebrush block copolymers offer rich opportunities for the design of complex hierarchical materials. As consequences of the densely grafted molecular architecture, bottlebrush polymers can adopt highly extended backbone conformations and exhibit unique physical properties. A recent report has described the unusual phase behavior of ABC bottlebrush triblock terpolymers bearing grafted poly(D,L-lactide) (PLA), polystyrene (PS), and poly(ethylene oxide) (PEO) blocks (LSO). In this work, a combination of resonant soft X-ray reflectivity (RSoXR), near edge X-ray absorption fine structure spectroscopy (NEXAFS), and self-consistent field theory (SCFT) was used to provide insight into the phase behavior of LSO and underlying backbone chain conformations. Consistent with SCFT calculations, RSoXR measurements confirm a unique mesoscopic ACBC domain connectivity and decreasing lamellar periods (d 0) with increasing backbone length of the PEO block. RSoXR and NEXAFS demonstrate an additional unusual feature of brush LSO thin films: when the overall film thickness is ~3.25d 0, the film-air interface is majority PS (>80%). Since PS is the midblock, the triblocks must adopt looping configurations at the surface, despite the preference for the backbone to be extended. This result is supported by backbone concentrations calculated through SCFT, which suggest that looping midblocks are present throughout the film. Collectively, this work provides evidence for the flexibility of the bottlebrush backbone and the consequences of low-χ block copolymer design. We propose that PEO blocks localize at the PS/PLA domain interfaces in order to screen the highest-χ contacts in the system, driving the formation of loops. These insights introduce a potential route to overcome the intrinsic penalties to interfacial curvature imposed by the bottlebrush architecture, enabling the design of unique self-assembled materials.

Multimodal Characterization of the Morphology and Functional Interfaces in Composite Electrodes for Li-S Batteries by Li Ion and Electron Beams.

We report the characterization of multiscale 3D structural architectures of novel poly[sulfur-random-(1,3-diisopropenylbenzene)] copolymer-based cathodes for high-energy-density Li-S batteries capable of realizing discharge capacities >1000 mAh/g and long cycling lifetimes >500 cycles. Hierarchical morphologies and interfacial structures have been investigated by a combination of focused Li ion beam (LiFIB) and analytical electron microscopy in relation to the electrochemical performance and physicomechanical stability of the cathodes. Charge-free surface topography and composition-sensitive imaging of the electrodes was performed using recently introduced low-energy scanning LiFIB with Li+ probe sizes of a few tens of nanometers at 5 keV energy and 1 pA probe current. Furthermore, we demonstrate that LiFIB has the ability to inject a certain number of Li cations into the material with nanoscale precision, potentially enabling control of the state of discharge in the selected area. We show that chemical modification of the cathodes by replacing the elemental sulfur with organosulfur copolymers significantly improves its structural integrity and compositional homogeneity down to the sub-5-nm length scale, resulting in the creation of (a) robust functional interfaces and percolated conductive pathways involving graphitic-like outer shells of aggregated nanocarbons and (b) extended micro- and mesoscale porosities required for effective ion transport.

Mechanical Response of Thermally Annealed Nafion Thin Films.

Perfluorinated ionomers, in particular, Nafion, are a critical component in hydrogen fuel cells as the ion conducting binder within the catalyst layer in which it can be confined to thicknesses on the order of 10 nm or less. It is well reported that many physical properties, such as the Young's modulus, are thickness dependent when the film thickness is less than 100 nm. Here we utilize a cantilever bending methodology to quantify the swelling-induced stresses and relevant mechanical properties of Nafion films as a function of film thickness exposed to cyclic humidity. We observe a factor of 5 increase in the Young's modulus in films thinner than 50 nm and show how this increased stiffness translates to reduced swelling or hydration. The swelling stress was found to increase by a factor of 2 for films approximately 40 nm thick. We demonstrate that thermal annealing enhances the modulus at all film thicknesses and correlate these mechanical changes to chemical changes in the infrared absorption spectra.

Analytical Multimode Scanning and Transmission Electron Imaging and Tomography of Multiscale Structural Architectures of Sulfur Copolymer-Based Composite Cathodes for Next-Generation High-Energy Density Li-S Batteries.

Poly[sulfur-random-(1,3-diisopropenylbenzene)] copolymers synthesized via inverse vulcanization represent an emerging class of electrochemically active polymers recently used in cathodes for Li-S batteries, capable of realizing enhanced capacity retention (1,005 mAh/g at 100 cycles) and lifetimes of over 500 cycles. The composite cathodes are organized in complex hierarchical three-dimensional (3D) architectures, which contain several components and are challenging to understand and characterize using any single technique. Here, multimode analytical scanning and transmission electron microscopies and energy-dispersive X-ray/electron energy-loss spectroscopies coupled with multivariate statistical analysis and tomography were applied to explore origins of the cathode-enhanced capacity retention. The surface topography, morphology, bonding, and compositions of the cathodes created by combining sulfur copolymers with varying 1,3-diisopropenylbenzene content and conductive carbons have been investigated at multiple scales in relation to the electrochemical performance and physico-mechanical stability. We demonstrate that replacing the elemental sulfur with organosulfur copolymers improves the compositional homogeneity and compatibility between carbons and sulfur-containing domains down to sub-5 nm length scales resulting in (a) intimate wetting of nanocarbons by the copolymers at interfaces; (b) the creation of 3D percolation networks of conductive pathways involving graphitic-like outer shells of aggregated carbons;

Elemental Sulfur and Molybdenum Disulfide Composites for Li-S Batteries with Long Cycle Life and High-Rate Capability.

The practical implementation of Li-S technology has been hindered by short cycle life and poor rate capability owing to deleterious effects resulting from the varied solubilities of different Li polysulfide redox products. Here, we report the preparation and utilization of composites with a sulfur-rich matrix and molybdenum disulfide (MoS2) particulate inclusions as Li-S cathode materials with the capability to mitigate the dissolution of the Li polysulfide redox products via the MoS2 inclusions acting as "polysulfide anchors". In situ composite formation was completed via a facile, one-pot method with commercially available starting materials. The composites were afforded by first dispersing MoS2 directly in liquid elemental sulfur (S8) with sequential polymerization of the sulfur phase via thermal ring opening polymerization or copolymerization via inverse vulcanization. For the practical utility of this system to be highlighted, it was demonstrated that the composite formation methodology was amenable to larger scale processes with composites easily prepared in 100 g batches. Cathodes fabricated with the high sulfur content composites as the active material afforded Li-S cells that exhibited extended cycle lifetimes of up to 1000 cycles with low capacity decay (0.07% per cycle) and demonstrated exceptional rate capability with the delivery of reversible capacity up to 500 mAh/g at 5 C.

Comparison of Nanoscale Focused Ion Beam and Electrochemical Lithiation in ß-Sn Microspheres.

The development of Li focused ion beams (Li-FIB) enables controlled Li ion insertion into materials with nanoscale resolution. We take the first step toward establishing the relevance of the Li-FIB for studies of ion dynamics in electrochemically active materials by comparing FIB lithiation with conventional electrochemical lithiation of isolated ß-Sn microspheres. Samples are characterized by cross-sectioning with Ga FIB and imaging via electron microscopy. The Li-FIB and electrochemical lithiated Sn exhibit similarities that suggest that the Li-FIB can be a powerful tool for exploring dynamical Li ion-material interactions at the nanoscale in a range of battery materials.

Inverse Vulcanization of Elemental Sulfur to Prepare Polymeric Electrode Materials for Li-S Batteries.

Sulfur-rich copolymers based on poly(sulfur-random-1,3-diisopropenylbenzene) (poly(S-r-DIB)) were synthesized via inverse vulcanization to create cathode materials for lithium-sulfur battery applications. These materials exhibit enhanced capacity retention (1005 mAh/g at 100 cycles) and battery lifetimes over 500 cycles at a C/10 rate. These poly(S-r-DIB) copolymers represent a new class of polymeric electrode materials that exhibit one of the highest charge capacities reported, particularly after extended charge-discharge cycling in Li-S batteries.

Visualization of phase evolution in model organic photovoltaic structures via energy-filtered transmission electron microscopy.

The morphology of the active layer in an organic photovoltaic bulk-heterojunction device is controlled by the extent and nature of phase separation during processing. We have studied the effects of fullerene crystallinity during heat treatment in model structures consisting of a layer of poly(3-hexylthiophene) (P3HT) sandwiched between two layers of [6,6]-phenyl-C61-butyric acid methyl ester (PCBM). Utilizing a combination of focused ion-beam milling and energy-filtered transmission electron microscopy, we monitored the local changes in phase distribution as a function of annealing time at 140 °C. In both cases, dissolution of PCBM within the surrounding P3HT was directly visualized and quantitatively described. In the absence of crystalline PCBM, the overall phase distribution remained stable after intermediate annealing times up to 60 s, whereas microscale PCBM aggregates were observed after annealing for 300 s. Aggregate growth proceeded vertically from the substrate interface via uptake of PCBM from the surrounding region, resulting in a large PCBM-depleted region in their vicinity. When precrystallized PCBM was present, amorphous PCBM was observed to segregate from the intermediate P3HT layer and ripen the crystalline PCBM underneath, owing to the far lower solubility of crystalline PCBM within P3HT. This process occurred rapidly, with segregation already evident after annealing for 10 s and with uptake of nearly all of the amorphous PCBM by the crystalline layer after 60 s. No microscale aggregates were observed in the precrystallized system, even after annealing for 300 s.

Anisotropic, hierarchical surface patterns via surface wrinkling of nanopatterned polymer films.

By combining surface wrinkling and nanopatterned polymer films, we create anisotropic, hierarchical surfaces whose larger length-scale (wrinkling wavelength) depends intimately on the geometry and orientation of the smaller length-scale (nanopattern). We systematically vary the pattern pitch, pattern height, and residual layer thickness to ascertain the dependence of the wrinkling wavelength on the nanopattern geometry. We apply a composite mechanics model to gain a quantitative understanding of the relationship between the geometric parameters and the anisotropy in wrinkling wavelength. Additionally, these results shed light on the effect of surface roughness, as represented by the nanopattern, on the metrology of thin films via surface wrinkling.

Molecular order in high-efficiency polymer/fullerene bulk heterojunction solar cells.

We report quantitative measurements of ordering, molecular orientation, and nanoscale morphology in the active layer of bulk heterojunction (BHJ) organic photovoltaic cells based on a thieno[3,4-b]thiophene-alt-benzodithiophene copolymer (PTB7), which has been shown to yield very high power conversion efficiency when blended with [6,6]-phenyl-C71-butyric acid methyl ester (PC(71)BM). A surprisingly low degree of order was found in the polymer-far lower in the bulk heterojunction than in pure PTB7. X-ray diffraction data yielded a nearly full orientation distribution for the polymer π-stacking direction within well-ordered regions, revealing a moderate preference for π-stacking in the vertical direction ("face-on"). By combining molecular orientation information from polarizing absorption spectroscopies with the orientation distribution of ordered material from diffraction, we propose a model describing the PTB7 molecular orientation distribution (ordered and disordered), with the fraction of ordered polymer as a model parameter. This model shows that only a small fraction (≈20%) of the polymer in the PTB7/PC(71)BM blend is ordered. Energy-filtered transmission electron microscopy shows that the morphology of PTB7/PC(71)BM is composed of nanoscale fullerene-rich aggregates separated by polymer-rich regions. The addition of diiodooctane (DIO) to the casting solvent, as a processing additive, results in smaller domains and a more finely interpenetrating BHJ morphology, relative to blend films cast without DIO.

Correlations between mechanical and electrical properties of polythiophenes.

The elastic moduli of polythiophenes, regioregular poly(3-hexylthiophene) (P3HT) and poly-(2,5-bis(3-alkylthiophene-2-yl)thieno[3,2-b]thiophene) (pBTTT), are compared to their field effect mobility showing a proportional trend. The elastic moduli of the films are measured using a buckling-based metrology, and the mobility is determined from the electrical characteristics of bottom contact thin film transistors. Moreover, the crack onset strain of pBTTT films is shown to be less than 2.5%, whereas that of P3HT is greater than 150%. These results show that increased long-range order in polythiophene semiconductors, which is generally thought to be essential for improved charge mobility, can also stiffen and enbrittle the film. This work highlights the critical role of quantitative mechanical property measurements in guiding the development of flexible organic semiconductors.